Organic phosphorus compounds,compositions containing same,and uses thereof



nited States Patent Ofice 3,518,200 Patented June 30, 1970 12 Claims ABSTRACT OF THE DISCLOSURE A detergent composition is described containing an organo-methylene diphosphonic compound having the formula wherein R is selected from the class consisting of aliphatic hydrocarbyl, alicyclic, aryl, alkaryl, and aralkyl groups of from 5 to carbon atoms and X is selected from the class consisting of hydrogen ions, alkali metal ions, ammonium ions and amine ions; as well as a dry cleaning composition containing an ester of an organo-methylene diphosphonic acid having the formula X0 H- OX wherein R is selected from the class consisting of aliphatic hydrocarbyl, alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and X is selected from the class consisting of aliphatic hydrocarbyl, aryl, alkaryl and aralkyl groups of from 1 to 30 carbon atoms.

This application is a continuation-in-part of application Ser. No. 271,607, filed Apr. 9,1963, now US. Pat. No. 3,299,123.

This invention relates to organic compounds of phosphorus, compositions containing said compounds, and uses thereof.

An object of this invention is to provide new and useful organic compounds of phosphorus containing a group in their molecules.

A further object of this invention is to provide new and useful organic compounds of phosphorus containing a group in their molecules with the group being a hydrophobic and/or lipophilic group.

A further object of this invention is to provide new and useful organophosphonic acids, as well as their salts and esters.

A more specific object of this invention is to provide new and useful organo-methylene diphosphonic acids or the salts thereof which exhibit, among other things, combined surfactancy sequestering and defiocculating properties.

A more specific object of this invention is to provide new and useful organo-methylene diphosphonate esters which exhibit, among other things, the unique ability of solubilizing water in water immiscible solvents.

Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonic acids or the salts thereof.

Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonic acids or the salts thereof which are suitable for use in aqueous systems.

Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonate esters.

A still further object of this invention is to provide detergent compositions containing organo-methylene diphosphonate esters which are suitable for use as drycleaning detergents in organic solvents.

Other objects of this invention will appear from the description hereinafter.

This invention is directed to new and useful organomethylene diphosphonic acid compounds, as well as the salts and esters thereof, said compounds having the general formula Xo\( R (fit/0X P P Xo 1'1 OX wherein: R is selected from the class consisting of aliphatic hydrocarbyl, alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and X is selected from the class consisting of cations selected from the group of hydrogen ions, alkali metal ions, ammonium ions and amine ions, and aliphatic hydrocarbyl, aryl, alkaryl and aralkyl groups of from 1 to 30 carbon atoms. Preferably, the aliphatic hydrocarbyl group represented by R contains from 7 to 30 carbon atoms. when the symbols R and X represent groups containing carbon chains, such as aliphatic hydrocarbyl groups, or groups containing alkyl moieties, i.e., aralkyl groups, such carbon chains may be of a straight chain structure or branched chain structure. For the symbols R. and X when they represent aliphatic hydrocarbyl groups, such groups may be saturated or unsaturated. The above mentioned groups which are represented by R can also contain substituents, such as, hydroxyl, halides, i.e., fluoride, chloride, bromide and iodide, alkoxyl groups, ester groups, ether groups, nitro groups sulfonyl groups, amide groups, amino groups, carboxyl groups, nitroso groups, and the like as long as they do not materially interfere with the hydrophilic and/ or lipophilic nature of groups. For most end use applications the compounds of the instant invention should preferably contain not more than 25 carbon atoms associated with R and X (when X represents ester groups), and there are few, if any, end uses, in which the foregoing groups contain more than a total of 50 carbon atoms.

These compounds can be characterized quite generally as having a PCP linkage in their molecules and are generically described in this specification by the general terms organo-methylene diphosphonic acids, the salts of organo-methylene diphosphonic acids, and the esters of organo-methylene diphosphonic acids.

The compounds of the invention can be prepared by various methods with the following methods presented as being representative of their preparation.

The ester of the organo-methylene diphosphonic acids can be prepared by first forming a metallo-derivative of a methylene diphosphonate ester and reacting this metallo-ester derivative with an organo-halide to produce the desired organo-methylene diphosphonate ester. The

reaction of the metallo-ester derivative with the organohalide is believed represented by the following equation:

(2) MCH PO (ester) +hal-R- RCH [PO (ester 2 +Mhal wherein R represents the same groups as in the foregoing general Formula 1.

In general, metallo-derivatives of the tetra-ester methylene diphosphonate can be prepared in several ways. When preparing the Group IA (alkali metals) ester derivatives and particularly the sodioand potassio-ester derivatives it is usually only necessary to react the alkali metal directly with the ester. The reaction is often exothermic so that, in most cases, it may be necessary to bring the reactants together while cooling, to dilute the mixture with an inert solvent such as xylene, benzene, toluene, ether, dioxane, hexane and the like, or to add the sodium or potassium slowly to the esters in the inert solvent. In some cases it may be necesary to employ all of the immediately foregoing procedures. It is usually advantageous to heat the reaction mixture for the last few minutes of the reaction, however, in order to facilitate the reaction. The Group IIA (alkaline earth metals) and in particular the calcium and magnesium metals can, in most cases, be reacted with the tetra-ester of the methylene diphosphonate in the presence of pyridine with the higher esters requiring in most cases moderate heating for completion of the reaction. In some cases, it is also possible to prepare the Group I-B metal derivatives, and in particular the silver-ester derivative and cuprous-ester derivative; the Group IIB metal derivatives, and in particular the zinc-ester derivative; and Group IV-A metal derivatives, and in particular the leadand tin-ester derivatives by methods which are similar to the foregoing methods. Because of the relative inexpensiveness and the ready availability of sodium and potassium and because of their rather straight forward reaction with the ester it is generally advantageous to form the sodioand potassio-ester derivatives and therefore, sodium and potassium are the preferred metals for use in forming these ester derivatives.

In general, the reaction of the metallo ester derivatives with an organo halide, i.e., reaction (2), is relatively straight forward. Often times, however, it may be necessary to use temperatures above room temperature, i.e., about 25 C., in order to facilitate the reaction with temperatures of between about 70 C. to about 180 C. usually being sufiicient. In most cases, depending on the temperature used, a definite precipitate forms, i.e., metalhalide, after a period of time of between about 10 minutes and about 4 hours. The precipitate may be removed by several Well known methods, such as, filtration, contrifugation and decantation, or by dissolution with water and phase separation, and, if desired, the filtrate can thereafter be distilled to improve the purity of the organomethylene diphosphonate ester.

It may be necessary, however, when using organo halides containing substituent groups, such as, hydroxyl, carboxylic acid, and halides, to protect these groups during the reaction. Usually the carboxylic acid groups can be protected by the well-known method of esterification prior to the reaction and hydrolysis of the ester subsequent to the reaction. Also the hydroxyl group can usually be protected by the well known method of ether formation using such materials as dihydropyrane, benzyl chloride, tritychloride and the like to form the ethers followed by removal of the protective groups by such methods as hydrolysis with dilute mineral acids, catalytic hydrogenation, or chemical reduction. In addition, by using well-known methods the halide group of polyhalide compounds can usually be protected by conversion into an ether group, a common reactant being sodium alkoxide, and the ether group subsequently cleaved with a hydrogen halide to remove the protective ether groups.

The organo-methylene diphosphonic acid can be prepared by the hydrolysis of the corresponding esters with a concentrated mineral acid. Generally, by refluxing the ester and a concentrated mineral acid, such as, HCl or HBr, at reflux temperatures for a period of usually about five hours is all that is necessary for the hydrolysis.

The salts of the organo-methylene diphosphonic acids can be prepared by neutralization of the acids with a stoichiometric amount of a base or a salt of a volatile acid that contains essentially the desired cation. Bases or salts of volatile acids such as those containing an alkali metal, ammonia and amines are especially suited. For example, to make a sodium salt, one of organo-methylene diphosphonic acids can be neutralized with a stoichiometric amount of a base containing the sodium cation, such as NaOH, Na CO and the like. It should be noted that organo-methylene diphosphonic acid titrates using a pH meter as a tribasic acid, however, the tetra salts can be prepared by neutralization of the acids with a stoichiometric amount of a base and evaporating to dryness. In addition, it has been found if the acids are titrated using a pH meter in the presence of a 10% NaCl solution they will titrate as tetra-basic acids.

The following examples are presented to illustrate the invention, with parts by weight being used in the examples unless otherwise indicated.

EXAMPLE 1 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 288 grams tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 65 C. After all of the potassium is used up about 179 grams of n-hcptyl bromide is added dropwise to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated between about C. and C. for about 10 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester as a colorless liquid. Analysis of the P N.M.R. spectra of the ester indicates tetraethyl octylidene diphosphonate, C'1H15CH[PO(OC2H5)2]2 with a small amount of impurity 5%) of tetraethyl methylene diphosphonate. Elemental analysis yields the following results.

Calculated (percent): C, 49.80; H, 9.39. Found (percent): C, 46.82; H, 9.51.

EXAMPLE 2 The ester prepared according to Example 1 is hydrolyzed to the acid by refluxing about 386 grams with about 600 ml. concentrated HCl for about 5 hours. Evaporation to dryness yields the acid, octylidene diphosphonic acid, C H CH[PO(OH) The equivalent weight of this product, by titration, is found to be about 98.0 which compares favorable with the calculated value of about 91.3. Elemental analysis yields the following results.

Calculated (percent): C, 35.00; H, 7.29. Found (percent): C, 33.l7; H, 6.89.

EXAMPLE 3 Trisodium octylidene diphosphonate C H CH[PO(ONa) [PO(ONa) (OH) is prepared by dissolving about 274 grams of free acid obtained as in Example 2 in about 1.2 liters of 10% NaOH solution and evaporating the aqueous solution to dryness at about 140 C. with the anhydrous form of the salt being formed.

EXAMPLE 4 Into a suitable reaction vessel about 39.1 grams potassiummetal is added slowly to about 288 grams tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 65 C. After all of the potassium is used up about 247 grams of n-dodecylbromide is added dropwise to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated at about 120 C. for about 4 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester as a colorless liquid. Analysis of the P N.M.R. spectra of the ester indicated tetraethyl tridecylidene diphosphonate,

Elemental analysis of this product yields the following results.

Calculated (percent): C, 55.3; H, 10.2; P, 13.6. Found (percent): C, 54.28; H, 10.58; P, 12.97.

EXAMPLE 5 Tetraethyl tridecylidene diphosphonate is hydrolyzed to the acid by refluxing about 454 grams with about 600 ml. of concentrated HCl for about 2 to 3 hours. Evaporation to dryness yields the acid, tridecylidene diphosphonic acid, C H CH[PO(OH) which is analyzed with the following results.

Calculated (percent): C, 43.4; H, 8.78; P, 17.99. Found (percent): C, 44.86; H, 8.71; P, 17.90.

EXAMPLE 6 Tri-ammonium tridecylidene diphosphonate,

is prepared by dissolving about 334 grams of the free acid obtained as in Example 5 in about 1% liters of *NH OH solution and evaporating the aqueous solution to dryness at about 120 C. with the anhydrous form of the salt being formed.

EXAMPLE 7 Into a suitable reaction vessel about 102 grams of 3- c-hloro-3-methyl pentane is added slowly to a potassiobutyl ester derivative reaction mixture prepared as in Example 1. To ensure a satisfactory degree reaction the mixture is heated at about 120 C. for about 6 hours. After filtering the potassium chloride, the reaction product is purified by distillation yielding tetrabutyl fi-diethyl- ,B-methylethylidene diphosphonate,

7 EXAMPLE 8 Disodium cyclohexyl methylene diphosphonate,

is prepared by dissolving about 322 grams of the free acid (cyclohexyl methylene diphosphonic acid), prepared generally by procedures used in Example 2, in about 1 liter of 11.5% NaOH solution and evaporating the aqueous solution to dryness at about 120 C. with the anhydrous form of the salt being formed.

EXAMPLE 9 Tetraethyl benzyl methylene diphosphonate C6H4CH[P(O)-(OC2H5)2]2 prepared generally by the procedures used in Example 1, is hydrolyzed to the acid by refluxing about 347 grams of the ester with about 800 ml. of concentrated HCl for about 4 hours. Evaporation to dryness yields the acid, benzyl methylene diphosphonic acid,

EXAMPLE l0 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 479 grams tetraphenyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 70 C. After all of the potassium is used up about 233 grams of 2-bromobipheny1 is added slowly 6 to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated at about C. for about 8 hours. After filtering the potassium bromide, the reaction product is distilled yielding the ester, tetraphenyl biphenyl methylene diphosphonate,

EXAMPLE l1 Tetraethyl dodecylbenzyl methylene diphosphonate, (C H )C H CH[PO(OC H h, prepared generally by procedures used in Example 1, is hydrolyzed to the acid by reuflxing about 425 grams of the ester with about 800 ml. of concentrated HCl for about 4 hours. Evaporation to dryness yields the acid, dodecylbenzyl methylene diphosphonic aCid, (C12H25)C6H4CH[PO(OH)2]2- I EXAMPLE 12 Tetraethyl acetophenone methylene diphosphonate CH C(O)C H -CH[PO(OC H prepared generally by procedures used in Example 1, is hydrolyzed to the acid by refluxing about 405 grams of the ester with about 800 ml. of concentrated HCl for about 3 hours. Evaporation to dryness yields the acid, acetophenone methylene diphosphonic acid, CH C (O C H CH [PO (OH) EXAMPLE l3 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 288 grams of tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 70 C. After all of the potassium is used up about 333 grams of octadecylbromide is added slowly to the reaction mixture. To ensure a satisfactory degree reaction the mixture is heated at about 120 C. to 140 C. for about 10 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester, tetraethyl nonadecylidene diphosphonate,

Elemental analysis of the product gives the following result.

Calculated (percent): C, 60.5; H, 11.73. Found (percent): C, 63.07; H, 11.49.

Nuclear magnetic resonance analysis gives a P shift in p.p.m. of -23.9.

EXAMPLE l4 Into a suit-able reaction vessel about 39.1 grams of potassium metal is added slowly to about 288 grams of tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 70 C. After all of the potassium is used up about grams of ot-chloropyrrole is added slowly to the reaction mixture. To ensure a satisfactory degree reaction the mixture is heated at about C. to about C. for about 6 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester, tetraethyl pyrryl-l-methylene diphosphonate,

Other methylene diphosphonate esters which can be reacted with metallic sources to form the metallo-ester derivatives, such as the potassio-ester derivatives, according to the procedures as illustrated by the foregoing examples include the following esters: tetramethyl methylene diphosphonate, tetra-n-hexyl methylene diphosphonate, tetera-iso-propyl methylene diphosphonate, tetradodecyl methylene diphosphonate, tetrahexadecyl methylene diphosphonate, tetra-toluyl methylene diphosphonate, tetra-xylyl methylene diphosphonate, and the like, as well as mixed esters, such as, diethyl-dibutyl methylene diphosphonate, diethyl-di-n-hexyl methylene diphosphonate, dimethyl-diethyl methylene diphosphonate and the like.

Other halide compounds which can be reacted with the metallo-ester derivatives, such as the potassio-ester deriva tives, according to procedures as illustrated by the foregoing example to form compounds of the instant invention include aliphatic hydrocarbyl halide compounds, such as, 3-chloro-2-methyl bntene-l; 3-chloro-2-methyl butene- 2; 2 chloro 2-methyl pentane; 3-chloro-2,2-dimethyl butane; 4-chloro-2,2-dimethyl butane; 3-chloro-2,2,3-tri methyl butane; 3-chlorohexane; n-hexyl chloride; n-undecyl chloride; n-hexadecyl chloride; n-hexyl bromide; n-octyl bromide; n-dodecyl bromide; n-tetradecyl bromide; l-bromo-n-caproic acid; 2-bromo hexanoic acid and the like.

Alicyclic halide compounds include cyclopentyl bromide, cyclohexyl chloride, cycloheptanyl chloride, cycloheptanyl bromide, cyclopentadiene dibromide, cyclohexane carboxylic acid chloride, l-chloro-l-methyl cyclohexane, 3-bromo-cyclohexene, 3-chloro-cyclohexene, 2'- chloro-cyclopentadiene, 2-bromo-cycloheptanone, l-2-dibromo cycloheptane, 1-bromo-4-tert-butyl-cyclohexane, 1 chloro 1 methyl cyclohexane, 1-2-dibromo-cycloheptane, l-chloro-3-methyl cyclohexane, and the like.

Aryl halide compounds include the mono-cyclic arylhalide compounds, such as, chlorobenzene, 2-ch1oroaniline, 2-amin0-4, 6'dichloro phenol bromobenzene, 4- bromo aniline and the like, as well as the polycyclic aryl halide compounds, such as, 3-chloro-biphenyl, 4-amino- 4'-chloro biphenyl, 2-chloro-1-napthal, 2-chloro-anthraquinone, l-chloro-napthalene, l-bromo'napthalene, 2- bromo biphenyl, and the like.

Alkaryl halide compounds include benzyl chloride, B-phenyl ethyl chloride, 4-methyl benzyl chloride, 3- methyl benzyl chloride, Z-methyl benzyl chloride, 2- chlorobenzyl chloride, 4-chlorobenzyl chloride, 3-chlorobenzyl chloride, 4-isopropyl benzyl chloride, m-xylene dichloride, wchloro acetophenone, benzyl chloroformate, benzyl bromide, fl-phenyl ethyl bromide, 2-bromo benzyl bromide, 3-nitro benzyl bromide and the like.

Aralkyl halide compounds include 2-chlorotoluene, 3- chlorotoluene, 4-chlorotoluene, l-chloro-Z-ethyl benzene, 2-chloro-2-vinyl benzene, l-chloro-Z-isopropyl benzene, 2- chloro-4-isopropyl-l-methyl benzene, p-chloro benzoic, acid, 2-chloro-4-octyl phenol, 2-chloro-4-nonyl phenol, 2- chloro-4-dodecyl phenol, 2-benzyl-4-chlorophenol, 2- bromotoluene, l-bromo-4-ethyl benzene, 4-bro-moacetanilide, 4-bromo-acetophenone, phenaryl bromide, 4-bromobenzoic acid and the like.

Other bases or salts of volatile acids which can be reacted with the free acids to produce salt compounds of the instant invention according to the procedures as illutrated by the foregoing examples include the inorganic alkali metal and ammonium salts, oxides and hydroxides,

' such as NaCl, NaNO Na O, Na CO KOH, K 0, KCl,

K CO KNO LiOH, LiCl, LiNO Li CO CsOH, CsCl, CSNOg, (252003, NH4C1, NH4NO3, (].-II'I4)2CD()3, NHOH, and amines, such as, ethyl amine, diethylamine, propyl amine, propylene diamine, diethylene triamine, hexyl amine, Z-ethylhexyl amine and the like.

Quite unexpectedly organo-methylene diphosphonic acids or the salts thereof were found to exhibit not only good deflocculating or dispersing properties and sequestration properties but also good surfactancy properties. It is highly unusual for all of these properties to be effectively exhibited by the same compound. As can be appreciated, such compounds can advantageously be utilized in applications which can use the foregoing properties, such as, detergent compositions. In many detergent applications such as textile cleaning including synthetic textiles and hard surface cleaning, the ability of the detergent composition to remove the soil, keep the soil suspended in the washing medium, as well as, exerting a water softening effect in the washing medium by sequestration of calcium and magnesium ions, is of paramount importance.

The higher alkylidene diphosphonic acids or the salts thereof are preferred in applications which use the combined surfactancy, sequestration and defiocculating properties. These compounds are of the following formula:

wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl radicals containing from 5 to 20 carbon atoms (preferably 7 to 20 carbon atoms) and Z is a cation selected from the group consisting of hydrogen, alkali metal ions, ammonium ions, and amine ions.

As used in detergent compositions, the compounds of the instant invention are preferably formulated with other compounds which may include other surface active compounds (actives) as well as builders such as sodium tripolyphosphate and tetrapotassium pyrophosphate, antiredeposition agents such as carboxymethyl cellulose and the like, brightening agents, perfumes and the like, in amounts between about 5% to 50% by weight of the detergent composition. The resulting detergent composition is generally effective when used in aqueous systems in conventional amounts such as is normally used with detergent compositions and which is generally about 5% concentration or below.

As being illustrative of builders which can be used with the compounds of the instant invention are organic builder materials which include amino polycarboxylic acids, the amino tri(lower alkylidenephosphonic) acids, the alkylene diphosphonic acids, the water soluble salts of the foregoing acids and mixtures thereof.

Amino polycarboxylic acids are presented by the general structure GHzCOOH N-CHzCOOH where R is a member selected from the group consisting of the radicals CCOOH Rr R2 o-oo0H wherein R is a member selected from the group consistmg of hydrogen, lower alkyl (l4 carbon atoms), hydroxy substituted lower alkyl, phenyl and hydroxy substituted phenyl, and R is a member selected from the group consisting of hydrogen, lower alkyl (1-4 carbon atoms), and hydroxy substituted lower alkyl.

Compounds illustrative of the amino polycarboxylic acids include nitrilo triacetic acid, ethylenediamine tetraacetic acid, diethylenetriamine penta-acetic acid, 1:2:diaminocyclohexane tetra-acetic acid, hydroxyethyl amino diacetic acid, hydroxyethyl ethylene diamine triacetic acid, orthohydroxyl phenyl ethylene diamine triacetic acid, anthanilic-N-N-diacetic acid, tris(hydroxymethyl) diethylene triamine diacetic acid, c-dibutyl-nitrilo triacetic acid and c-cyclohexenyl-nitrilo triacetic acid.

Amino tri(lower alkylidene phosphonic acids) are represented by the general structure where X and Y are members selected from the group consisting of hydrogen and lower alkyl groups (1-4 carbon atoms).

Compounds illustrative of amino tri(lower alkylidenephosphonic) acids include amino tri(methylenephosphonic) acids amino tri(ethylidenephosphonic acid), amino tri (isopropylidenephosphonic acid), amino tri (butylidenephosphonic acid), amino tri(propylidenephosphonic acid), amino tri(tert-amylidenephosphonic acid), amino tri(isoamylidenephosphonic acid) and amino tri sec-butylidenephosphonic acid) Alkylene phosphonic acids are represented by the general structure HO E X (])/0 i HO Y 11 OH where X is a member selected from the group consisting of hydrogen and lower alkyl group (l-4 carbon atoms), Y is either hydrogen, hydroxyl, a halogen, especially chlorine, bromine and fluorine, or lower alkyl group (1-4 carbon atoms), and rt is an integer from 1 to 6.

Compounds illustrative of alkylene diphosphonic acids include methylenediphosphonic acid; ethylidenediphosphonic acid; 1 hydroxyl, ethylidenediphosphonic acid; hexamethylenediphosphonic acid; isopropylidenediphosphonic acid, butylidenediphosphonic acid; hydroxylmethylenediphosphonic acid; 1 hydroxyl, propylenediphosphonic acid; amylidenediphosphonic acid; pentamethylenediphosphonic acid; penta(propylidene)diphosphonic acid; tetra(l-hydroxyethylidene)diphosphonic acid.

It is to be understood that although the sodium salts of the amino tri(lower alkylidenephosphonic acids), alkylenediphosphonic acids, and aminopolycarboxylic acids are preferred, other water soluble salts such as potassium, lithium, and the like, as well as mixtures of the alkali metal salts may be substituted therefor. In addition, the ammonium salts, as well as amine salts, may be used to practice this invention.

Compounds illustrative of these salts include monopotassium nitrilotriacetate; pentasodium diethylenetriamine pentaacetate; diammonium ethylenediaminetetraacetate; dimethylamino diethylenetriaminetetra-acetate; trilithium nitrilotriacetate; disodium diethylenetriamine penta-acetate; tripotassium ethylenediaminetetra-acetate; diethylamino nitrilotriacetate; pentapotassium diethylenetriamine penta-acetate; monosodium nitrilotriacetate; tetrasodium ethylenediaminetetra-acetate; disodium amino tri(methylphosphonate); dipotassium amino tri(methylphosphonate); diammonium amino tri(methylphosphonate); pentasodium amino tri(methylphosphonate); dilithium amino tri(ethylidenephosphonate); diammonium amino tri(ethylidenephosphonate); pentasodium amino tri (isopropylidenephosphonate); pentapotassium amino tri (butylidenephosphonate); diammonium amino tri(isopropylidenephosphonate) disodium amino tri(butylidenephosphonate); diethylamine amino tri(methylphosphonate; dimethylamine amino tri(ethylidenephosphonate); monolithium methylenediphosphonate; dipotassium methylenediphosphonate; diethylamine methylenediphosphonate; triammonium methylenediphosphonate; tetrasodium methylenediphosphonate; trisodium l-hydroxy ethylidenediphosphonate; trisodium tri(2-hydroxy, 3 amylidene) diphosphonate; monopotassium ethylidenediphosphonate; dimethylamine ethylenediphosphonate; tripotassium amylidenediphosphonate; tetrasodium butylidenediphosphonate; diammonium isopropylidenephosphonate; monosodium amylidenediphosphonate; and tripotassium ethylidenediphosphonate.

As being further illustrative of builders which can be used with the compounds of the instant invention are inorganic builder materials, usually comprised of inorganic phosphates, carbonates, sulfates, silicates or combinations thereof, and, in particular, the alkali metal salts of the foregoing materials. The alkali metal salts are preferably the potassium and sodium salts, although ammonium salts may be employed, particularly in combination with the potassium or sodium salts. The phosphate compounds are preferably the chain polyphosphates. Such polyphosphates contain more than 1 phosphorus atom per molecule, as distinguished from orthophosphates which contain only one phosphorus atom per molecule. Chain polyphosphates are non-cyclic (and usually linear) phosphates, as distinguished from ring or cyclic phosphates such as trimetaphosphates and tetrametaphosphates. Examples of the more common chain polyphosphates are tetrapotassium. pyrophosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, potassium hexametaphosphate and sodium hexametaphosphate.

Another builder material which is preferably utilized along with the chain polyphosphates are the water-soluble sodium and potassium silicates. As is well-known, so dium silicates can vary quite widely in composition, ranging from tetra and disilicates having a mole ratio of Na O:SiO of 1:4 and 1:2, respectively, to the more alkaline silicates, such as the orthosilicate having a mole ratio of Na O:SiO of 2:1. In general, sodium silicate (Na O:SiO =1 :2) is the preferred. silicate compound for use according to the present invention. However, other silicates, or mixtures of silicates, having an overall mole ratio of Na O:SiO between about 1:1 and 1:4 can be used. The carbonates and sulfates are preferably the sodium and potassium carbonates and sulfates.

Ordinarily at least about 5 percent of the builder material by weight of the total composition can be used and usually not over about 90 percent with the preferred range being between about 30 and about percent by weight. Additionally, minor amounts, usually less than about 2 percent by weight of the total composition, of additives, such as dyes, perfumes, anti-redeposition agents (sodium carboxymethyl cellulose) and the like can be incorporated into the composition.

Although the detergent compositions of this invention may comprise an organo-methylene diphosphonic acid or salt thereof and the above-described builder materials and other additives, the compositions may also contain relatively minor amounts, usually less than 15% by weight, preferably 1 to 10% by weight, on a solids basis, of other organic surface active agents such as foaming agents, emulsifiers, detergent surfactants or the like. Examples of organic surface active agents include anionic surfactants such as sulfated and sulfonated alkyl, aryl, and alkyl aryl hydrocarbons and alkali metal salts thereof, for example, sodium salts of long chain alkyl sulfates, sodium salts of alkyl naphthalene sulfonic acids, sodium salts of sulfonated abietenes, sodium salts of alkyl benzene sulfonic acids particularly those in which the alkyl group contains from 8-24 carbon atoms; sodium salts of sulfonated mineral oils and sodium salts of sulfosuccinic acid esters such as sodium dioctyl sulfos uccinate.

Advantageous anionic surfactants include the higher alkyl aryl sulfonic acids and their alkali metal and alkaline earth metal salts such as for example sodium dodecyl benzene sulfonate, sodium tridecyl benzene sulfonate, magnesium dodecyl benzene sulfonate, potassium tetradecyl benzene sulfonate, ammonium dodecyl toluene sulfonate, lithium pentadecyl benzene sulfonate, sodium dioctyl benzene sulfonate, disodium dodecyl benzene disulfonate, disodium di-isopropyl naphthalene disulfonate and the like as Well as the alkali metal salts of fatty alcohol esters of sulfuric and sulfonic acids, the alkali metal salts of alkyl aryl (sulfothioic acid) ethers and the alkyl thiosulfuric acid, etc. Preferred anionic organic surface active agents are, as noted hereinbefore, sodium salts of alkyl benzene sulfonic acids and particularly preferred sodium salts of alkyl benzene sulfonic acids are those in which the alkyl group or radical contains to 18 carbon atoms in a straight (i.e. unbranched) chain.

Examples of nonionic surfactants include products formed by condensing one or more alkylene oxides of 2 to 4 carbon atoms, such as ethylene oxide or propylene oxide, preferably ethylene oxide alone or with other alkylene oxides, with a relatively hydrophobic compound such as a fatty alcohol, fatty acid, sterol, a fatty glyceride, a fatty amine, an aryl amine, a fatty mercapian, tall oil, etc. Nonionic surface active agents also include those products produced by condensing one or more relatively lower alkyl alcohol amines (such as methanolamine, ethanolamine, propanolamine, etc.) with a fatty acid such as lauric acid, cetyl acid, tall oil fatty acid, abietic acid, etc. to produce the corresponding amide.

Particularly advantageous nonionic surface active agents are condensation products of a hydrophobic compound having at least 1 active hydrogen atom and a lower alkylene oxide (for example the condensation product of an aliphatic alcohol containing from about 8 to about 18 carbon atoms) and from about 3 to about mols of ethylene oxide per mol of the alcohol, or the condensation product of an alkyl phenol containing from about 8 to about 18 carbon atoms in the alkyl group and from about 3 to about 30 mols of ethylene oxide per mol of alkyl phenol. Other advantageous nonionic detergents include condensation products of ethylene oxide with a hydrophobic compound formed by condensing propylene oxide with propylene glycol.

Other typical examples of these catagories of the anionic and nonionic surface active agents are described in Schwartz and Perry, Surface Active Agents, Interscience Publishers, New York (1949) and the Journal of water at room temperature. The compounds tested were at concentrations believed representative of detergent concentrations used in actual applications. The results of the test are tabulated below.

TAB LE 1 Surface tension (dyne/cm.) at indicated molar concentrations As can be observed from the above table, compounds illustrative of the invention, i.e., (2) and (3), exhibit the ability to lower the surface tension of water (4). Compounds (2) and (3) compared very favorably with sodium dodecylbenzene sulfonate (5), a widely used surfactant, when used in molar concentrations of 5x10 and 10- It should be noted that compound (1) exhibited no appreciably surfactancy ability since a compound exhibiting a surface tension above about at molar concentrations of 5 1O and 10* is not usually regarded as a surfactant. As can be appreciated, therefore, by reason of their surfactancy, compounds of this invention are particularly Well suited for use in detergent compositions.

Compounds illustrative of the invention were tested for deflocculating properties in a carefully controlled kaolin slurry. The kaolin used in the evaluation was essentially free of impurities and was placed in an aqueous slurry with a solids content about 68%. The slurry throughout the evaluation was maintained at a pH of about 7 with NaOH or HCl. The apparent viscosity was determined with a Stormer viscometer at 300 rpm. The results of the tests are tabulated below.

TABLE 2 Apparent viscosity in centipoises at 300 r.p.m. Stormer at indicated weight percent of deflocculating agent on a dry clay basis American Oil Chemists Society, vol. 34, No. 4, pp. 170- 216 (April 1957).

The detergent composition of the present invention is not to be limited to any particular method of mixing the ingredients used in the compositions. The organo-methylene diphosphonic acids or salts may be mechanically mixed in, crutched in the detergent composition in the form of a slurry, or dissolved in a solution of the detergent composition. In addition, the organo-methylene diphosphonic acids or salts may be admixed with other ingredients in any of the forms in which the detergent composition is manufactured in, as well as being added simultaneously or separately to an aqueous solution. In any event, the organo-methylene diphosphonic acids or salts are intended to be used with the other ingredients at the time of application as a cleansing agent.

Compounds illustrative of the invention were tested for surfactancy properties by determining surface tension measurements with a Du Nuoy tensiometer in distilled As can be observed from the above table, minor amounts of the compounds illustrative of the invention, i.e., (2) and (3) deflocculated a plastic slurry into a flowable slurry. In addition, compounds (2) and (3) compared Wery favorably with sodium tripolyphosphate (4), a widely used deflocculant, and compound (1) when used in amounts of about .1 and .15 weight based on a dry clay basis.

Compounds illustrative of the invention were tested for sequestration properties. The conditions of the test were to dissolve .25 gm. of the tetrasodium salt of the compound of the instant invention and .25 gm. of Na C- O in 250 ml. of water and adjust the pH to 12 with NaOH. To the solution is added 0.1 M Ca(NO until a cloudy endpoint, i.e., the precipitation of CaC O- is achieved. In order to calculate the pounds of calcium sequestered by pounds of material tested, the volume of 0.1 M Ca(NO used, in cc. units, is multiplied by 1.6. The results of the test are tabulated below.

13 TABLE 3 Lbs. calcium/ 100 lbs. Compound: of compound (1) Tetrasodium octylidene diphosphonate C H CH[PO(ONa) 4-8 (2) Tetrasodium tridecylidene diphosphonate C1gH25CH[PO(ONa)2] 1.0

As can be observed from the above table, compounds illustrative of the instant invention, i.e. (1) and (2) exhibited the ability to sequester calcium, thus indicating their beneficial use in aqueous systems containing such 1011s.

The following detergent formulations in which the percentages are by weight are presented as being illustrative of the present invention:

Percent Tetrasodium tridecylidene diphosphonate 20 Sodium tripolyphosphate 50 Sodium carboxymethyl cellulose 1 Sodium silicate 10 Sodium sulfate 19 Tetrasodium octylidene diphosphonate 20 Trisodium l-hydroxy, ethylidene diphosphonate 30- Sodium carboxymethyl cellulose 1 Sodium silicate 10 Sodium sulfate 19 Sodium tripolyphosphate 20 Trisodium pentadecylidene diphosphonate 20 Trisodium nitrilo triacetate 30 Sodium silicate 10 Sodium carbonate 40 Tetrapotassium tridecylidene diphosphonate 5 Tetrasodium octylidene diphosphonate 5 Sodium dodecyl benzene sulfonate Pentasodium amino tri(methylphosphonate) 30 Sodium carboxymethyl cellulose 1 Sodium sulfate 49 Percent Tetrasodium octadecylene diphosphonate 20 Nonionic condensate (dodecyl alcohol-ethylene oxide on a 1:10 molar ratio basis) 10 Tetrapotassium pyrophosphate 30 Sodium silicate 39 Sodium carboxymethyl cellulose 1 All of the foregoing detergent formulations are effective for cleaning textiles, hard surfaces such as dishes, walls and the like when used in concentrations of about 0.2% in water.

The esters of organo-methylene diphosphonic acids were found not only to be substantially miscible with water but also highly soluble in organic solvents, such as hydrocarbon solvent, i.e. hexane and pentane, carbon tetra chloride, haloethylene solvents (perchloroethylene), ethers, alcohols, and the like. Also, the esters were found to impart a solubilizing action to water in water-immiscible solvents, such as many of the previously mentioned solvents. This totally unexpected property renders them high- 1y useful as gasoline de-icer additives and along with their surfactancy properties renders them useful as dry cleaning detergents. As can be appreciated, however, the unique ability to impart a solubilizing action to Water in waterimmiscible solvents can be utilized in many and varied applications and, therefore, the foregoing mentioned applications are merely indicative of their use.

The esters of higher alkylidene diphosphonic acids are preferred in applications which use the combined surfactancy and/or water solubilizing properties. These compounds are of the following formula:

wherein R is selected from the class consisting of satu rated and ethylenically unsaturated aliphatic hydrocarbyl radicals containing from 5 to 20 carbon atoms (preferably 7 to 20 carbon atoms) and R R R and R are selected from the class consisting of alkyl groups of from 1 to 20 carbon atoms, aryl hydrocarbyl groups and alkaryl groups with the lower alkyl groups being especially preferred.

Because of the complexity of the ternary solubility diagram of the esters of the instant inventionwaterwater-immiscible solvents the following is set forth for example purposes only.

A solution of 10 cc. of hexane and 5 cc. of the following esters of the higher alkylidene diphosphonic acids dissolves the amounts of water at room temperature indicated in Table 4. The water Was added dropwise until permanent cloudiness or phase separation was observed. The tabulated results are presented. in the following table.

TABLE 4 Compound: H 0 added (cc.)

(1) Tetra ethyl octylidene diphosphonate C H CH[P0(OC H .5 (2) Tetra ethyl tridecylidene diphosphonate C H CH[PO(OC H 2.5

It should be noted that the foregoing example solutions exhibited no phase separation at the end of a one week period of standing nor was there a phase separation after the solutions had been centrifuged at 5,000 rpm. for one hour indicating that the water was completely dissolved in the water-immiscible solvent. It should further be noted that tetraethyl methylene diphosphonate, CH [PO(OC H did not impart a solubilizing action to Water in a Water-immiscible solvent.

As dry cleaning additives the ester compounds of the instant invention can be used as either the primary surfactant or in conjunction with other surfactants. When used as substantially the primary surfactant with many of the common organic solvents, such as, Stoddards solvent (petroleum distillate) and perchloroethylene, amounts within the range of .05 to 10% by weight are usually sufficient with amounts of from about 1% to about 2% by weight being preferred.

What is claimed is:

1. A detergent composition consisting essentially of an amount of at least about 5% by weight of said composition of an organo-methylene diphosphonic compound having the formula wherein R is selected from the class consisting of (a) aliphatic hydrocarbyl groups containing from 7 to 30 carbon atoms, (b) alicyclic hydrocarbyl groups containing from 5 to 7 carbon atoms, (c) aryl groups selected from the group consisting of monocyclic, dicyclic, or tricyclic hydrocarbon groups containing from 6 to 18 carbon atoms, (d) amino-substituted aryl groups wherein the aryl portion is the same as that defined in item (c), (e) alkaryl groups wherein the aryl portion of said group is the same as that defined in item (c) and the alkyl portion of said group contains from 1 to 12 carbon atoms, and (f) all of the groups defined in items (a), (b), (c), (d) and (e) containing a halogen substituent, and X is selected from the class consisting of hydrogen ions, alkali metal ions, ammonium ions and amine ions,

1 5 and a builder material in an amount of at least about 5% by weight of said composition.

2. A detergent composition according to claim 1, wherein said compound has the following formula wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl groups containing from 7 to 20 carbon atoms and X is selected from the class consisting of hydrogen ions, alkali metal ions, ammonium ions and amine ions.

3. A detergent composition according to claim 2, wherein said compound is a sodium salt of tridecylidene diphosphonate.

4. A detergent composition according to claim 2, wherein said compound is a sodium salt of octylidene diphosphonate.

5. A detergent composition according to claim 2, wherein said compound is present in amounts of from about 5% to 50% by weight of said composition.

6. A detergent composition according to claim 2, wherein there is present a builder material in amounts of from about 5% to 90% by weight of said composition.

7. A detergent composition according to claim 2, wherein there is present an organic surface active agent selected from the group consisting of anionic and nonionic surface active agents in amounts less than about 15% by weight of said composition.

8. A dry cleaning composition consisting essentially of an amount of at least about 0.05% by weight ofvsaid composition of an ester of an organo-methylene diphosphonic acid, said ester having the formula t I X H 0X wherein R is selected from the class consisting of (a) aliphatic hydrocarbyl groups containing from 7 to 30 carbon atoms, (b) alicyclic hydrocarbyl groups containing from to 7 carbon atoms, (c) aryl groups selected from the group consisting of monocyclic, dicyclic, or tricyclic hydrocarbon groups containing from 6 to 18 carbon atoms, (d) amino-substituted aryl groups wherein the aryl portion is the same as that defined in item (c), (e) alkaryl groups wherein the alkyl portion of said group is the same as that defined in item (c) and the alkyl portion of said group contains from 1 to 12 carbon atoms, and (f) all of the groups defined in items (a), (b), (c),

(d) and (e) containing a halogen substituent, and X is selected from the class consisting of (a) aliphatic hydrocarbyl groups containing from 7 to 30 carbon atoms, (b) aryl groups selected from the group consisting of monocyclic, dicyclic or tricyclic hydrocarbon groups containing from 6 to 18 carbons atoms, (c) alkaryl groups wherein the aryl portion of said group is the same as that defined in item (b) and the alkyl portion of said group contains from 1 to 12 carbon atoms, and an elfective amount of a dry cleaning organic solvent.

9. A dry cleaning composition according to claim 8, wherein said ester is a higher alkylidene diphosphonic acid which functions substantially as a detergent, said ester having the formula R30 0 R 0 OR: may R4O/ 1 1 ORz wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl groups containing from 7 to 20 carbon atoms, and R R R and R are selected from the class consisting of alkyl groups of from 1 to 20 carbon atoms, aryl hydrocarbyl groups selected from the group consisting of monocyclic, dicyclic or tricyclic hydrocarbon groups contain ing from 6 to 18 carbon atoms and alkaryl groups wherein the aryl portion of said group is the same as defined above and the alkyl portion of said group contains from 1 to 12 carbon atoms.

10. A dry cleaning composition according to claim 9, wherein said detergent is present in amounts of from about .05 to 10% by weight of said composition.

11. A dry cleaning composition according to claim 10, wherein said detergent is tetraethyl octylidene diphosphonate.

12. A dry cleaning composition according to claim 10, wherein said detergent is tetraethyl tridecylidene diphos phonate.

References Cited UNITED STATES PATENTS 3,299,123 1/1967 Fitch et al. 260-O 3,169,930 2/1965 Gedge 252-137 LEON D. ROSDOL, Primary Examiner D. L. ALBRECHT, Assistant Examiner US. Cl. X.R.

37 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,518 ,200 Dated June so 1970 Steven Josevn Pitch and Riyad R. Irani Inventofl a) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 9 line H the "C" in the structure should be an O Signed and sealed this 2nd day of May 1972.

(SEAL) Attest:

EDJARD M.FLETCHER, JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents 

